Isothiazolylazo dyes

ABSTRACT

Compounds of the general formula I ##STR1## where X is unsubstituted or substituted alkyl, cycloalkyl, aralkyl or aryl, Y is chlorine, bromine, carbamyl or cyano, Z is hydrogen, carbamyl, cyano or acetyl, R is hydrogen or C 1  -C 3  -alkyl, R 1  and R 3  independently of one another are each hydrogen or unsubstituted or substituted alkyl, alkenyl, cycloalkyl, aralkyl or aryl, R 2  is hydrogen or unsubstituted or substituted alkyl and R 1  and R 2 , together with the nitrogen atom, form a saturated 5-membered or 6-membered ring, are particularly useful for dyeing textile fibers.

This is a continuation-in-part of application Ser. No. 641,580, filedAug. 17, 1984, abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to compounds of the general formula I##STR2## where X is unsubstituted or substituted alkyl, cycloalkyl,aralkyl or aryl, Y is chlorine, bromine, carbamyl or cyano, Z ishydrogen, carbamyl, cyano or acetyl, R is hydrogen or C₁ -C₃ -alkyl, R¹and R³ independently of one another are each hydrogen or unsubstitutedor substituted alkyl, alkenyl, cycloalkyl, aralkyl or aryl, R² ishydrogen or unsubstituted or substituted alkyl and R¹ and R², togetherwith the nitrogen atom, form a saturated 5-membered or 6-membered ring.

2. Description of the Preferred Embodiments

Examples of radicals X are C₁ -C₈ -alkyl which can be substituted bychlorine, bromine, cyano, hydroxyl, C₁ -C₄ -alkoxy, phenoxy, C₁ -C₈-alkoxycarbonyl, unsubstituted or substituted phenyl, carbamyl or amino,and C₅ -C₇ -cycloalkyl, and phenyl which is unsubstituted or substitutedby fluorine, chlorine, bromine, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy.

Specific examples of radicals X are: ##STR3## where T is F, Cl, Br, CH₃,OCH₃ or OC₂ H₅.

Examples of radicals R¹ and R³ are:

1. Unsubstituted or substituted alkyl, such as CH₃, C₂ H₅, n-C₃ H₇,CH(CH₃)₂, n-C₄ H₉, CH₂ -CH(CH₃)₂, ##STR4##

2. Unsubstituted or substituted cycloalkyl radicals: ##STR5##

3. Unsubstituted or substituted aralkyl radicals: ##STR6##

4. Unsubstituted or substituted phenyl radicals: C₆ H₅, C₆ H₄ CH₃, C₆ H₃(CH₃)₂, C₆ H₄ OCH₃, C₆ H₃ (OCH₃)₂, C₆ H₄ Cl and C₆ H₂ (OCH₃)₂ Cl;

5. The radicals CH₂ CH═CH₂, CH₂ COOCH₃, (CH₂)₅ COOCH₃, (CH₂)₅ COOC₂ H₅,(CH₂)₅ COOC₄ H₉, ##STR7## where n is 2, 3, 4 or 6.

6. Acyloxyradicals: (CH₂)₂ OCHO, (CH₂)₂ OCOCH₃, (C₂ H₄ O)₂ CHO (C₂ H₄O)₂ COCH₃, (CH₂)₂ OCOC₃ H₇, ##STR8## (CH₂)₂ OCONHC₆ H₄ Cl and (CH₂)₂OCONHC₆ H₃ Cl₂ and the corresponding radicals containing (CH₂)₃, (CH₂)₄or (CH₂)₆ instead of (CH₂)₂.

7. Acyl radicals: CHO, CH₃ CO, C₂ H₅ CO, C₃ H₇ CO, ##STR9## C₂ H₅ CO,CH₃ C₆ H₄ CO, C₆ H₅ CH₂ CO, C₆ H₅ OCH₂ CO, CH₃ SO₂, C₂ H₅ SO₂, C₆ H₅ SO₂and CH₃ C₆ H₄ SO₂.

Examples of preferred substituents are hydrogen, C₂ H₅, CH(CH₃)₂, n-C₄H₉, CH₂ --CH(CH₃)₂, ##STR10##

Examples of radicals R², in addition to hydrogen, are ##STR11##

Examples of radicals formed by R¹ and R² together with the nitrogen atomare: ##STR12##

Depending on their structure, the compounds of the formula I aresuitable, for example, as disperse dyes for synthetic polyesters, astransfer dyes for dyeing thermoplastic materials consisting of, forexample, polystyrene, polyethylene, polypropylene, nylon or their blockpolymers, and for dyeing cotton and union fabrics of cotton andpolyesters, for example by the method described in German Patent No.1,811,796.

As a rule, very fast dyeings and prints are obtained.

The dyes are as a rule further distinguished by good color build-upsubstantially independent of the pH-value of the dyeing bath.

Particularly important compounds are those of the formula Ia ##STR13##where B is methyl or isopropyl, or is phenyl or benzyl which isunsubstituted or substituted by methyl, methoxy, chlorine or bromine,and R¹ and R³ have the above meanings. R¹ is preferably phenyl which isunsubstituted or substituted by methyl, methoxy, chlorine or bromine.Particularly preferred dyes of the formula Ia are those in which B andR¹ are each phenyl which is unsubstituted or substituted by methyl,methoxy, chlorine or bromine, and R³ is one of the abovementionedradicals which is bonded to the amino group via a secondary carbon atom.

The compounds of the formula I can be prepared by reacting a diazoniumcompound of an amine of the formula ##STR14## with a coupling componentof the formula ##STR15## by a conventional method.

The Examples which follow illustrate the reactions. Parts andpercentages are by weight, unless stated otherwise.

EXAMPLE 1

20.1 parts of 5-amino-4-cyano-3-phenylisothiazole in a mixture of 150parts by volume of a 17:3 glacial acetic acid/propionic acid mixture and70 parts of 80% strength sulfuric acid are stirred, and 32 parts ofnitrosylsulfuric acid (11.5% of N₂ O₃) are added slowly at 15°-20° C.The mixture is stirred for 3 hours at this temperature and in thepresence of an excess of nitrous acid, and stirring is then continuedfor a further 15 minutes in the presence of 5 parts of urea. Theresulting diazo solution is then run into a solution of 34 parts of2-(2-methoxyphenylamino)-3-cyano-4-methyl-6-cyclohexylaminopyridine in300 parts by volume of glacial acetic acid and 150 parts by volume ofdimethylformamide, and stirring is continued at 15° C. until coupling iscomplete, which takes about 30 minutes. Filtration under suction andwashing with 300 parts by volume of glacial acetic acid and with hotwater give the dye of the formula: ##STR16## as an aqueous paste(λmax.=533 nm). A union fabric consisting of 63 parts of polyester and37 parts of cotton is impregnated, at pH 6, with a formulationconsisting of 6 parts (based on dry substance) of this dye, 80 parts ofpolyethylene glycol having a molecular weight of 1,500, 20 parts of areaction product obtained from 1 mole of hexamethylenediamine and 15moles of ethylene oxide and 894 parts of water. The impregnated fabricis dried at 110° C. and then treated with hot air at 215° C. for 5minutes. It is washed with cold water, and the dyeing is treated with acommercial detergent at 100° C. A very lightfast, washfast, brilliantbluish red dyeing which is fast to solvents and to crocking is obtainedin this manner.

EXAMPLE 2

If, using the preparation conditions described in Example 1, 20.1 partsof 5-amino-4-cyano-3-phenylisothiazole are diazotized and the product iscoupled to 32 parts of2-(2-ethylhexyloxyprop-3'-ylamino)-3-cyano-4-methyl-6-aminopyridine, adye of the formula ##STR17## is obtained (λmax=511 nm).

A polyester/cotton union fabric is printed with a formulation consistingof 10 parts of the dye from Example 2, 100 parts of a reaction productobtained from polyethylene oxide having a molecular weight of 300 withboric acid in a molar ratio of 3:1, 30 parts of oleic aciddiethanolamide and 860 parts of a 3% strength alginate thickener, andthe print is dried at 110° C., treated with superheated steam at 185° C.for 5 minutes, washed with cold water and then washed with a commercialdetergent at 100° C. A lightfast, washfast reddish orange print on awhite ground is obtained, the print being fast to solvents.

On a pure cotton fabric, the same procedure gives a print which is ofthe same color and has equally good fastness properties.

The dyes in the Table below are obtained by similar procedure. They arepreferably used by the stated procedure, and give very fast dyeings andprints on polyesters and polyester/cotton blends, and in some cases alsoon pure cotton.

    __________________________________________________________________________     ##STR18##                                                                    Ex. No.                                                                            B          B.sup.1    B.sup.2    λ.sub.max.                       __________________________________________________________________________     3                                                                                  ##STR19##                                                                                ##STR20##                                                                                ##STR21## 532.5                                    4   "          "                                                                                         ##STR22## 533                                      5   "                                                                                         ##STR23##                                                                                ##STR24## 536                                      6   "          "                                                                                         ##STR25## 535                                      7   "                                                                                         ##STR26##                                                                                ##STR27## 538.5                                    8   "          "                                                                                         ##STR28## 538                                      9                                                                                  ##STR29##                                                                                ##STR30## H          532.5                                   10                                                                                  ##STR31## "          "          532.5                                   11   "          "                                                                                         ##STR32## 538.5                                   12                                                                                  ##STR33##                                                                                ##STR34##                                                                                ##STR35## 534                                     13   "                                                                                         ##STR36## "          532.5                                   14   "          "          CH(CH.sub.3).sub.2                                                                       533                                     15   "          "                                                                                         ##STR37## 533                                     16   "                                                                                         ##STR38## C.sub.2 H.sub.4 OCH.sub.3                                                                534                                     17   "                                                                                         ##STR39## "          530.5                                   18   "                                                                                         ##STR40## C.sub.3 H.sub.6 OCH.sub.3                                                                535.5                                   19   "                                                                                         ##STR41## "          531.5                                   20   "                                                                                         ##STR42## C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6                                     H.sub.5    535                                     21   "                                                                                         ##STR43## "          531                                     22   "                                                                                         ##STR44##                                                                                ##STR45## 534.5                                   23   "                                                                                         ##STR46## "          530.5                                   24   "          "          H          526.5                                   25   "                                                                                         ##STR47##                                                                                ##STR48## 535                                     26   "          "                                                                                         ##STR49## 533                                     27   "                                                                                         ##STR50## "          532                                     28                                                                                  ##STR51##                                                                                ##STR52##                                                                                ##STR53## 535.5                                   29                                                                                  ##STR54## "          "          535.5                                   30   "          "                                                                                         ##STR55## 532.5                                   31                                                                                  ##STR56##                                                                                ##STR57##                                                                                ##STR58## 527.5                                   32                                                                                  ##STR59## "          "          527                                     33                                                                                  ##STR60##                                                                                ##STR61## "          528                                     34                                                                                  ##STR62## "          "          528                                     35                                                                                  ##STR63##                                                                                ##STR64##                                                                                ##STR65## 531.5                                   36                                                                                  ##STR66## "          "          532                                     37                                                                                  ##STR67##                                                                                ##STR68## "          532.5                                   38                                                                                  ##STR69## C.sub.2 H.sub.4 OCH.sub.3                                                                 ##STR70## 533                                     39   "          C.sub.3 H.sub.6 OCH.sub.3                                                                "          534                                     40                                                                                  ##STR71##                                                                                ##STR72##                                                                                ##STR73## 526.5                                   41                                                                                  ##STR74##                                                                                ##STR75## "          527                                     42                                                                                  ##STR76## "                                                                                         ##STR77## 531                                     43                                                                                  ##STR78##                                                                                ##STR79##                                                                                ##STR80## 532                                     44                                                                                  ##STR81## "          "          532                                     45                                                                                  ##STR82## "                                                                                         ##STR83## 531.5                                   46   "                                                                                         ##STR84##                                                                                ##STR85## 521.5                                   47                                                                                  ##STR86## "          "          522                                     48                                                                                  ##STR87##                                                                                ##STR88##                                                                                ##STR89## 522                                     49   "          "          CH(CH.sub.3).sub.2                                                                       522.5                                   50   "          "                                                                                         ##STR90## 521.5                                   51                                                                                  ##STR91##                                                                                ##STR92##                                                                                ##STR93## 522.5                                   52   "                                                                                         ##STR94## CH(CH.sub.3).sub.2                                                                       522                                     53   "                                                                                         ##STR95## H          510                                     54                                                                                  ##STR96## "          H          510                                     55                                                                                  ##STR97## "          H          508                                     56                                                                                  ##STR98##                                                                                ##STR99##                                                                                ##STR100##                                                                              540.5                                   __________________________________________________________________________

EXAMPLE 57

27 parts of the coupling product obtained from5-amino-4-cyano-3-phenylisothiazole and2-(2-methoxyphenylamino)-3-cyano-4-methyl-6-(β-hydroxyethylamino)-pyridineare stirred in a mixture of 500 parts by volume of monochlorobenzene, 12parts of phenoxyacetic acid and 2.5 parts of p-toluenesulfonic acid for3 hours at 100° C. until thinlayer chromatography shows that thereaction is complete. The reaction mixture is cooled, and the product ofthe formula ##STR101## is then filtered off under suction and washedwith methanol and with water. Using the dyeing conditions of Example 1,this product gives a brilliant bluish red dyeing with similar fastnessproperties.

EXAMPLE 58

16.2 parts of2-(2-methoxyphenylamino)-3-cyano-4-methyl-5-(3-phenyo-4-cyanoisobenzothiazol-5'-ylazo)-6-[(2-hydroxy-1-ethyl)-ethylamino]-pyridinein 150 parts by volume of pyridine are stirred at 50° C., and 13 partsof benzoyl chloride are added dropwise. Stirring is continued at 50° C.until esterification is complete. The mixture is filtered under suctionat room temperature, and the product is washed with ethanol and withwater to give the dye of the formula ##STR102## When it is used fordyeing polyester/cotton blends, this dye gives results similar to thoseof Example 1.

EXAMPLE 59

16.5 parts of the dye obtained from3-(4-methoxyphenyl)-4-cyano-5-aminoisothiazole and2-(2-methoxyphenylamino)-3-cyano-4-methyl-6-[(2-hydroxy-1-ethyl)-ethylamino]pyridineare stirred in 300 parts by volume of monochlorobenzene at 100° C. Thereaction is completed by the dropwise addition of 12 parts of phenylisocyanate and stirring for 5 hours at 100° C. The product is thenfiltered off under suction while hot and washed with ethanol to give thedye of the formula ##STR103## This dye dyes polyester/cotton blends inbrilliant bluish red hues.

EXAMPLE 60

7 parts of 3-methyl-4-cyano-5-aminoisothiazole are introduced into amixture of 40 parts by volume of glacial acetic acid, 20 parts of 85%strength sulfuric acid and 16 parts of nitrosylsulfuric acid (11.5% ofN₂ O₃) at from 0° to +5° C. The mixture is stirred for 3 hours at from0° to 5° C., after which excess nitrous acid is destroyed with 3 partsof urea. The resulting diazo solution is then run into a solution of16.5 parts of2-[(2-phenoxy-3-ethoxy)propylamino]-3-cyano-4-methyl-6-aminopyridine in200 parts by volume of acetic acid and 60 parts by volume of water atfrom 0° to 5° C. Coupling is complete after 2 hours. The product isfiltered off under suction, washed with 70% strength acetic acid anddried at 80° C. to give the dye of the formula ##STR104## as a dark redpowder, which dyes polyester material in orange hues with very goodallround fastness.

The disperse dyes below are obtained using preparation conditionssimilar to those of Example 1, 2 or 60. Among these dyes, those productswhich are free of aromatic or strongly polar substituents are preferablyused as transfer dyes.

    __________________________________________________________________________     ##STR105##                                                                   Ex.                                                                           No. B             B.sup.1     B.sup.2    λ.sub.max.                    __________________________________________________________________________    61  CH.sub.3      C.sub.2 H.sub.4 OCH.sub.3                                                                 C.sub.2 H.sub.4 OCH.sub.3                                                                514                                  62  CH.sub.3      C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.3 H.sub.6 OCH.sub.3                                                                516.5                                63  CH.sub.3                                                                                     ##STR106##                                                                                ##STR107##                                                                              516.5                                64  CH.sub.3      C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                          516                                  65  CH.sub.3      C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.4 OCH.sub.3                                                                515                                  66  CH.sub.3      C.sub.2 H.sub.5                                                                           C.sub.3 H.sub.6 OCH.sub.3                                                                515                                  67                                                                                 ##STR108##                                                                                  ##STR109## H          509                                  68                                                                                 ##STR110##   C.sub.2 H.sub.4 OC.sub.4 H.sub.9                                                          H          508.5                                69                                                                                 ##STR111##   C.sub.2 H.sub.4 OC.sub.4 H.sub.9                                                          H          510.5                                70                                                                                 ##STR112##   C.sub.2 H.sub.4 OCH.sub.3                                                                 H          509                                  71                                                                                 ##STR113##   C.sub.2 H.sub.4 OCH.sub.3                                                                 C.sub.2 H.sub.4 OCH.sub.3                                                                517                                  72                                                                                 ##STR114##   C.sub.2 H.sub.4 OCH.sub.3                                                                 C.sub.2 H.sub.4 OCH.sub.3                                                                519                                  73                                                                                 ##STR115##   C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.3 H.sub.6 OCH.sub.3                                                                519                                  74                                                                                 ##STR116##   C.sub.4 H.sub.9                                                                           H          509                                  75                                                                                 ##STR117##                                                                                  ##STR118## C.sub.3 H.sub.6 OCH.sub.3                                                                530                                  76  CH(CH.sub.3).sub.2                                                                           ##STR119## C.sub.3 H.sub.6 OCH.sub.3                                                                528                                  77                                                                                 ##STR120##                                                                                  ##STR121## C.sub.3 H.sub.6 OCH.sub.3                                                                532                                  78  CH.sub.3                                                                                     ##STR122## C.sub.3 H.sub.6 OCH.sub.3                                                                528                                  79  CH.sub.3                                                                                     ##STR123## C.sub.3 H.sub.6 OCH.sub.3                                                                531                                  80                                                                                 ##STR124##                                                                                  ##STR125## C.sub.2 H.sub.4 OCH.sub.3                                                                529.5                                81                                                                                 ##STR126##                                                                                  ##STR127##                                                                                ##STR128##                                                                              529                                  82  CH.sub.3      C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.2 H.sub.4 OH                                                                       516                                  83                                                                                 ##STR129##   C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.2 H.sub.4 OH                                                                       518                                  84                                                                                 ##STR130##   C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.2 H.sub.4 OH                                                                       520                                  85  CH.sub.3                                                                                     ##STR131## C.sub.2 H.sub.4 OH                                                                       526                                  86  CH.sub.3                                                                                     ##STR132## C.sub.3 H.sub.6 OH                                                                       528                                  87  CH.sub.3                                                                                     ##STR133## C.sub.3 H.sub.6 OH                                                                       531                                  88  CH.sub.3                                                                                     ##STR134## C.sub.3 H.sub.6 OH                                                                       535                                  89  CH.sub.3                                                                                     ##STR135## CH(CH.sub.3).sub.2                                                                       535.5                                90  CH.sub.3                                                                                     ##STR136## C.sub.2 H.sub.4 OH                                                                       528.5                                91  CH.sub.3                                                                                     ##STR137## CH(CH.sub.3).sub.2                                                                       531                                  92                                                                                 ##STR138##                                                                                  ##STR139## H          525                                  93  CH.sub.3                                                                                     ##STR140## H          521                                  94                                                                                 ##STR141##                                                                                  ##STR142## H          527                                  95  CH(CH.sub.3).sub.2                                                                           ##STR143## H          521.5                                96  CH.sub.3                                                                                     ##STR144## H          529                                  97  CH.sub.3                                                                                     ##STR145## C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OH                                                      527                                  98  CH.sub.3                                                                                     ##STR146## C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OH                                                      528                                  99  CH.sub.3                                                                                     ##STR147## C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OH                                                      532                                  100 CH.sub.3                                                                                     ##STR148## C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6                                     H.sub.5    528                                  101 CH.sub.3                                                                                     ##STR149## C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6                                     H.sub.5    531                                  102 CH.sub.3                                                                                     ##STR150## C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6                                     H.sub.5    532                                  103 CH.sub.3                                                                                     ##STR151##                                                                                ##STR152##                                                                              531                                  __________________________________________________________________________

The dyes below were also prepared by methods similar to those describedabove:

    __________________________________________________________________________     ##STR153##                                                                   Ex.                                                                           No.                                                                              B             B.sup.1      B.sup.2                                                                              λ.sub.max.                        __________________________________________________________________________    104                                                                               ##STR154##                                                                                  ##STR155##                                                                                 ##STR156##                                                                          530.5                                    105                                                                               ##STR157##                                                                                  ##STR158##                                                                                 ##STR159##                                                                          532.5                                    106                                                                               ##STR160##                                                                                  ##STR161##                                                                                 ##STR162##                                                                          532                                      107                                                                               ##STR163##                                                                                  ##STR164##                                                                                 ##STR165##                                                                          536                                      108                                                                               ##STR166##                                                                                  ##STR167##                                                                                 ##STR168##                                                                          535.5                                    109                                                                               ##STR169##                                                                                  ##STR170##                                                                                 ##STR171##                                                                          533                                      110                                                                               ##STR172##                                                                                  ##STR173##                                                                                 ##STR174##                                                                          532.5                                    111                                                                               ##STR175##                                                                                  ##STR176##                                                                                 ##STR177##                                                                          530                                      112                                                                               ##STR178##                                                                                  ##STR179##                                                                                 ##STR180##                                                                          529                                      113                                                                               ##STR181##                                                                                  ##STR182##  H      507.5                                    114                                                                               ##STR183##                                                                                  ##STR184##  H      508                                      __________________________________________________________________________

We claim:
 1. An isothiazolylazo dye of the formula ##STR185## wherein Xis unsubstituted or substituted alkyl, cycloalkyl, aralkyl or aryl,Y iscyano, Z is cyano, R is hydrogen or C₁ -C₃ -alkyl, R¹ and R³independently of one another are each selected from the group consistingof H; and C₁ -C₈ -alkyl and C₁ -C₈ -alkoxy-(C₁ -C₈) alkyl which areunsubstituted or substituted by hydroxyl, C₁ -C₈ -alkoxy, phenoxy orphenyl, and C₁ -C₈ -cycloalkyl, or phenyl which are unsubstituted orsubstituted by chlorine, bromine, methyl, ethyl, methoxy or ethoxy, R²is a group selected from hydrogen and alkyl, or R¹ and R², together withthe nitrogen atom, form a saturated 5-membered or 6-membered ring. 2.The compound of claim 1, having the formula ##STR186## wherein B isselected from the group consisting of methyl, isopropyl, phenyl andbenzyl; the phenyl and benzyl groups being unsubstituted or substitutedby methyl, methoxy, chlorine or bromine.